Indigoid dyestuff



Patented Feb. 5, 1935 PATENT/OFFICE Y-I DIG mmsewn! Ernst Stoecklin, Binningenin'ear Basel, Hans" Veragutht Basel, and Fritz'Gri'eshabeig'Riehen, near Basel, Switzerland, assignors to Society I of Chemical Industry n in Basle, Basel, Switzer- No Drawers" Application June 21, 1933; Serial l*l'o..6'7t6;9'78. In Switzerland July 15, 1932 TIClai ms; (Cl. 260-53) This invention relates to the" manufacture or unsymmetrical indigoid dyestuffs by'condensing a 4,7-dialkyl-3-h-ydroxythionaphthalene of the general formula i Alk iir-hydtoiwthiinnaphthenesotithe.general F'orJ- mula II are, for example, "g hydroxythionaphthene, 5- methyl d-chlbro{3 hydroxythionaphthene; -2+(para dimethylamino- -ani1, of 5- chloro-T-methyl 3 hydroxy'thi'onaphthene, 4- m'etliyl d-enlarger--31 liydroxythionaphthene; 2 10 I I I I I. f (para-"-dimethylamino -fi of 7 -ch1oro-'4',6-di, wherem X represents n h gnd methyf-3-hydi-oxythionaphthene obtainable y a t e treating the latter with paranitroso-dimeth \@=IuII ylaniline, 6 -chloro-3-hydroxythionaphthene 2- v I Z I I I I carboxylic acid,, 1,2-naphthioindoxyl, 2,1-naphp m ;r a v wa ting f r ex'ampl'e thionindoxyl, 2,3-naphthioindoxyl, 2;l'-anthra'- I E i I I cenethioindoxy'l and 2,3-'-anthraquinonethioin-i 1 1 I doxyl. l I H I a t The condensation takes takes place by heating I x H ICQQH I v I H51 the components in a solvent which may act as Hall' v condensing agent. ".q ti 1' a 1 The-dyestufisqthus obtained correspond with: the general formula-i. ,v y HBLII v I u I .I: I

with a 3-hydroxythionaphthene of the general 1 l formula 3 00 it .q'e

II: ,FR o=z s 30,. V v p e so? 11E Wm p sems any I wherein. X. represents hydrogen" or halogen 4 I I 4 :Ranaryl'radical] "7 The dyestuffs" of this invention dye very va-' 352 I rious tints and the dyeings obtained are charachas Same slgmncnw'w terized by vejx'y good'properties of fastness. The

' dyestuffs can be converted" by known methods I I I into leucoester salts-s v I l J The following examples illustrate the invenn I tion, the parts being by wei ht;

0: I I I I Exemplar I H I34 lfpartof 2= tpara-diinethylamino arm of;

If desired, the dyestuif thus obtained is treated i' 'id im d XY H P h 445, with a halogenatingfigent. I are heatedtoboi'lingwith 234.5 partsof' 1-'chloro-' 4I7 dia1ky1 3 ;hydmxytmbmphthnes f the 2,3-naphthionind0xyl 8000 parts of benzene. general formulatI are, tor example lfl-dimethyb w q atione is: complete the. dyestu f 0 7 3-hydroxythionaphthene, 4,7-diethyl 3-hydroxythelfflrmla H 1 v. s I

thionaphthene, '4,7-diethyl-5 chloroe3-hydroxy thi'onaphthenm; ttll' dimiet'lthytlj-d-c hi1 0 rio-3 hydroxythionaphthene,4;7-dimethyl:-5-btomo;-3 Y hydmxyth ienaphthenes-za-carbomic acid, 2'-= (para-diamethylamino-)ani1 of 4,7-dimethyl-5- chilnro li-hydroxythionaphthenei (which may be 5: made; for instandehy the' aetion uh aw-mtrose l a om dfl-dimethyl fi chlbroi-a-hw is filtered, washed and dried, 'lt is' a redviolet droxytlfionaphthene); 4 ,1 edimethyli- 5-chiorm powder, soluble. in concentrated sulfuric acid to thionaphthenequinone; ('whi'clmmay be made; for a green solution? It fo'rms an orange-brown vat example by saponifying the; 2-( para-dimethyl-- and dyes cottonfullblue violettints of'good fastness. K 7

aminee9: anilw of 1 ltil dnnetlml-efiechloner-whydroxyt'hionap hthene with dilute niineral acid);

and: the dichleri'de ot 4=,7-dimethyl'-'5-ch1oro-3- hyidmoxythionaphthene; which. is formed; by'

treating; the latter with amihalogenating agent.

' ished. After filtration, washing and drying the 1- dyestuif'of thefformula f1 f V is in the form of a brownish violet powder, soluble in'concentrated-sulfuric acidto a yellowish green Example 2 g 212.5 parts of 5-chloro 4,7-dimethyl-3-hydroxythionaphthene and 320 parts of 2-(para-dimethy1amin0-)anil of 5-chloro-7-methyl-3rhy droxythionaphthene are stirred in 520'0Jpa'rt'sw of benzene at about C. until condensation is fin isobtained in the form of a violet powder, soluble in concentratedsulfuric acid to a blue-green solution. 'In'a green yellow vat cotton is dyed .full

violetred tints of very good properties of fastness.

ixdmples g R2155 sis, of 5? cmo'rong-aiisetil tsmy droxythionaphthene and 326 p rser 2- (paraFdi- 'f methylamino-)anil of -6-ethoxy-3-hydroxythio naphthene are heated to boiling in 8000 parts of benzene until condensation complete The dyestuff of the formula J CH3.

is filtered, .washed and, dried, The -brilliant yellow: red powder dissolves in concentrated sul- 'furic acid to a grass green solutionand dyes cot-- ton in a greenyellow vat strong rose tints.

. V 7 Example 4 H 7 2125 parts of; 5;-chloro- 4,7-dimethyl-3 hydroxythionaphthene are stirred in 8000 parts of benzene with 330 parts of 2-(para-dimethylaminc-Janil V of 1,2 naphthioindoxyl at boiling temperature until condensationfis complete. The

filtered, washed and dried dyestuffof the formula solution and dyeing cotton in a green yellow vat dark Bordeauir red of verygood fastnessl i Example5 its parts or 4,7 dimetliyl 3 hydroxythionaph thene, 296 parts of 2-(para-dimethylamino-yanil a .of 7-methyl-3-hydro'xythionaphthene and 4000 parts of benzene are heatedtogether to boiling.

When formation of'the dyestuff is at an end, the

precipitate ,which has'been formed is filtered.- The dyestuffs of the formula I V CH: 7

1,990,256 is fan orangered"powder solubl mficbncritrated reddish-brown dyestufi of sulfuric acid to a green solution and-dyeing cot ton in a yellow vat rose tints. By action of an halogenating agent on this dyestufl there may be obtained, for example 4,7-dimethyl-5'-bromo-'7'- methyl bis-thionaphtheneindigo of the formula and 4;? 'dimethyl 5, 5'-dibromo-7'-methyl-bisr thionaphtheneindigo of the formula 1 "CH1 J r these dyestuffs acid to a green solution and dye cotton in a yellow very good properties of fastnessq,

vat brilliant red or bright Bordeaux red tints of Ezample 'fil 310 parts' of 2-(par'a -dimethylamino-) anilfof v t v H3 dissolve inconcentrated sulfuric 4,7-dimethyl-3-hydroxythionaphthene, obtain- 3 able by action of para nitroso-dimethylanillne on r ,g 4,7-dimethyl-3-hydroxythionaphthene and of I melting point 208 C., 200 parts of 2,1-naphththioindoxyl'and 5000 parts of alcohol are boiled together until condensation is complete. .The

the formula CH: K

on; s

dissolves in concentrated sulfuric acid to a. blue solution andidyescotton in a redrorangef vat beautiful yellowish red-brown tints of very good fastness to chlorine, washing, kier-boiling' and light.

Example-7 dissolves in concentrated sulfuric acid to a bright fastness: ,v i

green solution anddyes cotton in an orange brown f vat redviolettintsfof very good properties of When this dyestufl in V and the solution is treated with bromine there. is obtained a violet powder soluble in concentrated sulfuric acid to a brl'ghtgreen'solution and dyeing' cotton in la gold I yellow. v'at strongl blue 1 violet tints 'of very good fastnessi --'rne following table displays furt Y er examples 1,990,253 3 of dyestuiis obtainable insaccordance with thein- .t I Example 1:

3 0 1 5 parts of the; dyestuifjdescribed in Example 5 '2-i(para-'dimethylamino-)anilof 5-dilm-Mfl-dimethyHI-hydroxythionaphthene Color of the 8 8? 1. color of 3 2 f I and; dyestufl the vat g I. fi-chloro+metl1y1-3-hydroxythionaphthene. Rose. Green. Redlkliish- Bluish-rose. ye ow. l I II. 2,-1-naphththioindoxyl. Dark -Bor- Green. 3 Br'own- B1uish-Bor-- r l deaux red. orange. vdeaux red. 5-chloro-4,7-dimethyl-3-hydroxythiqnapthene and:

III. z-(para-dimethylamino-hnil of 6-ehloro-fi-methyl-il-hydroxythionaphtheiie.' Rosef '(li-"a-ss Greelalnish Yellow'ish red green. ye 0W. v1 15 IV. 2-(para-dimetl1ylamino-)anil of 8-ch1oro-1,2-1rapl1thioindoxy1. g Grey-violet; teen, .1 -Oa-11 ge- Red-violet.

, v i rown. V V.=2-(para-dimethylamino-)anil of 4,7-dimethyl-3-hydroxythionaphthene. i Bluish-rose. Green.- Pale yel- B1uishrose. ow. -'i, 2 (para-dimethylmnifio-ihnil of4,7-dimethyl-3 hydroxythionaphthene and:

VI. 4-methyl-6-choloro-3-hydl'oxyfihionaphthene. v Red. 7 "Green; Yellow. "Rose. v p VII. i-methyl-fi-chloro-3-hydroxythionapl thene+brcm1ne Red. Green. Yellow. Item. t

The dyestuffs Nos. I to VII of the table'corre- 1 are made into a pastelwith'20 parts of caustic spond with the following formulae:-

VII.

soda solution of 33 per cent. strength. The paste is mixed with 750,.p'arts of water at C. and 15 parts of sodium hydrosulfite, and the whole is allowed to stand for 30 minutes and then diluted to 2000 parts with water. Into this bathlat 60 C. are entered I00 iparts-of cotton; after about 7' 10 minutesx50 parts of common-salt are added and; dyeing is: continued for: hour at; 60 C.

The goods are then washed, oxidized in air for 30 mimiteaxrinsed 'andnsoaped. The cotton is thus dyedi very fast "blue violet tints. l For wool, silk and artificial 'SilkIthB dyein process mustcbv iouslysbe variedias .mayibe necessary. v a 1 a What we claim is: 7 1. Unsymmetrical indigoid dyestuffs of the general formula I All:

1 dyed pink to orange to red-brown to red to violet tints.

2. Unsymmetrical indigoid dyestuffs of the general formula wherein X represents halogen and R a benzene or naphthalene or anthracene radical, which products form pink to red-brown to red to violet powders which dissolve in concentrated sulfuric acid to blue to blue-green to green solutions, i yield with hydrosulfite and caustic soda solution yellow to red to brown vats from which cotton is dyed pink to orange to' red-brown to red to violet tints. I i 3.- Unsymmetrical n isr i u f .1 e general formula t CH: V

1' wherein R represents" al benzene ornaphthalene o1; anthracene radical, which products form pink 7 c to red-brownto-redto violet powders which dis-' green to green solutions, yield, withhydrosulflte t solve in concentrated sulfuric acid to blue to blue- 7 e and caustic sodasolution yellow to red to brown vats from 'which cotton is dyed red-brown to red to violet tints.

pink to orange to Unsymmetrical indigoid dyestuffs of the general. formula; v

r h 7 CH: V

wherein R represents a, naphthalene radical/which Y products form redbrown to'red to violet powders which dissolve'in concentratedsulfuric acid to blue to green solutions"; yield with hydrosulflte and causticsoda solutionyellow to orange brown to red vats from which cotton is dyed red-brown to red toviolet tints.

5. Unsymmetrical indigoid general'iormula.

dyestuffs of the wherein R represents a naphthalene radical whichproduct's form. red+brdwn to; red to violet powders which dissolve in concentrated-'rsulfuric gcid to blue to green'solutions, yield with hydrosulfite andcaustic' sodasolution yellow to orange brown to red vats from which cotton isdyed redbrown to red to violet tints.

V 6. The unsymmetrical indigoid dyestufi of the formula 4 w which'product-forms a red violet powder "which i dissolves in concentrated sulfuric acidto 'a. green solution, yields'with hydrosulfiteand caustic soda. solution on orange-brown vat from which cotton is dyed blue-violet tints. 1 7. The unsymmetrical indigoid dyestufl of the formula l t which product forms a dark {Bordeaux red 

